Clarifying agents for water

ABSTRACT

The use of compounds of polyvalent cations with aluminate, borate, and aluminosilicate anions has been found to provide improved clarification methods for aqueous suspensions. The use of these materials is much more effective than that of the corresponding conventional mono-valent cation compounds. A particularly effective form of these clarifying agents results when preparation is carried out by high temperature methods, including the fusion of the reactants. Recycling of the used clarifying agents is possible using these materials, especially when the flocculated solids are incinerated during the ultimate disposal step.

United States Patent 1191 Lang 1 1 Sept. 30, 1975 CLARIFYING AGENTS FOR WATER 3.101.317 8/1963 Starry 210/52 3.2 5. 2 2 [76] lnventor: John L. Lang, P.O. Box 1242. 8 849 H966 wummbe Midland. Mich. 48640 FOREIGN PATENTS OR APPLICATIONS 2 Filed: Feb. 22 1972 227.429 1/1926 United Kingdom 210/52 [211 App!- 228,336 Primary Eva/niner-Thomas G. Wyse Related US. Application Data 1 [63] Continuation-impart of Ser. No. 144.416. May 17. 1 1 ABSTRACT 1971, abundone The use of compounds of polyvalent cations with alup I 1 minate, borate, and aluminosilicate anions has been [52] 210,47 found to provide improved clarification methods for [51] C028 aqueous suspensions. The use of these materials is [58] Field Search-m 3 much more effective than that of the corresponding conventional mono-valent cation compounds. A particularly effective form of these clarifying agents re [56] References Cited sults when preparation is carried out by high tempera- UNITED STA E PATENTS ture methods. including the fusion of the reactants. 1.604.125 10/1926 Kern; 210/47 1 Recyclingpf the used clarifying agents is possible 1.872.262 8/1932 Evans. 210/51 using these materials, especially when the flocculated 1.872.263 8/1932 Evans 10/53 X solids are incinerated during the. ultimate disposal 1.940.409 12 1933 Fink 210/47 Step 2.310.009 2/1943 Baker et a1. 210/51 2.416.007 2/1947 1 Claim, No Drawings Joachim 21053 x "1 'CLARI'FYING AGENTS FoR WATER CROSSREFERENCES TO RELATED APPLICATIONS This is a continuation-in-part of 144,4l6file'd May I7, 1971, entitled Clarifying Agent's for Water,

abandoned. i

BACKGROUND OF THE INVENTION The problems involved in the purification of water. particularly'that containing suspended solids, has been the subject of much investigation for an extended period. This is especially true in the cases of municipal water supply, sewagetreatment, treatmentof'discharges from mineral dressing operations, food processing'plants, breweries, and many other operations which are directed toward mans existence and endeavor. Many materials have been used to aid in the purification of water and wastes from such operations.

'Some of'these are relatively old; the use of alum, ferric or ferrous salts alone or in conjunetion'with lime, sodium aluminate, soluble: starches, water soluble natural, modified, and synthetic polymers,-and the like are examples of such flocculating agents. Recently, much attention has been given to the use of natural gums arid synthetic high molecular weight polyelectrolytes, as typifiedby poly( acrylic acid and salts thereof, poly(vinylbenzene sulfonic acid) and salts thereof, poly(- maleic acid) and salts thereof, the water dispersible re-,

action products of nucleophilic reagents with polymers containing vinyl benzylchloride and bromide: poly(ethyleneimine), and many others. Relatively non-ionic polymers, as poly(acrylamide) have also foundwide application for use in water clarification". Most of these.

materials must be used in certain pH ranges, and in proportion to the solids content of the waste, etc., the maintenance ofwhich parom'eters may be di ffieu lt' duringcontinuous-basis operation.

SUMMARY OF THE INVENTION f.

The object'of this invention is to providea new water purification system.

suspended. solids from water at a rapid rate, and pro-i duces a satisfactorily clear supernatant portion which may be readily removed as purified water, thus greatly increasing the overall capacity of existing water purification installations. o

Another object of this invention is to provide flocculating and settling agents which are physiologically inlected from Groups II and VIlI-Series' l of the Periodic Table of Elements. These compounds are essentially those of polyvalent cations with anions such as aluminatc, poly-aluminate, aluminosilicate, poly aluminosilicate, borate, poly borate, and the like.

Group II of the Periodic Table of Elements includes magnesium, calcium, strontium, barium, zinc, and cadmium. Group VIII-Series 4 includes iron, cobalt, and

nickel.

The preferred embodiment of the invention comp'rises the use of finely ground fusionformed compounds of calcium, magnesium, and barium with aluminate, aluminosilicate, poly aluminosilicate, and polyborate anions.

Many of these materials are prepared by calcining, i.e., heating at temperatures at which water and carbon dioxide are at least partly expelled, of such raw materials as limestones, dolostones, dolomites, argillaceous limestones, argillaceous dolostones, marls, clays,

shales,rnetallurgical slags, and other materials containing silica, alumina, calcium, magnesium, barium, bo-

ron, iron, and chemically analogous elements,

An especially advantageous clarification agent of this type may be prepared by clinkering, i.e., fusion reaction, of a mixture of limestone, clay and bauxite, so as to prepare a material containing 28% or more of calcium aluminate, followed by pulverization of the cooled clinker.

The use of these new clarifying agents is easily carried out, usually by simply mixing the untreated water with either the dry pulverized clarifying agent or a slurry thereof in water, allowing flocculation to take place in a quiescent or gently agitated settling zone.

'and the purified water removed bydecantation, siphoning, pumping off, filtration or any of the known methods or combinations thereof.

An effective procedure involves the addition to the mixture of untreated water and clarifying agent of a ground mineral which has some ion-exchange capacity or characteristics.

Alternatively,'the untreated water can be mixed with the clarifying agent in proper proportions, clarification allowed to take place, the supernatant clarified water removed,and the mixture of the thus-concentrated solid contaminant water, and clarifying agent recycled added at each recycling stage. This recycle procedure produces extra volumes of clarified water, when using any of the separation procedures between cycles. Use of this procedure increases the solids content of the flocculated residue several fold, thus increasing the ef fective capacity of water treating plants when compared to conventional operation, also minimizing the volume of settled solids that must be dewatered, wetinc inerated, dried or transported for ultimate disposal. In the case of municipal waste treatment plants, this method of operation converts, for practical purposes, a secondary treatment plant into a tertiary stage treatment plant with little or no added capital costs, and also reduces'the volume of sludge requiring de-watering, wetor dry-incineration, or transportation for ultimate disposal.

Because of the inorganic nature of the material herein taught to be effective clarification agents, they can be recycled in another way; when incineration is used as the means for ultimate disposal, the ash therefrom contains the flocculating agent in rejuvenated or regenerated form. In some cases, the material is still in the form of particles sufficiently small as to be immediately re-useable at high levels of effectiveness; in other cases it may be fused into larger nodules which are nevertheless effective, but re-grinding restores the material to its original level of effectiveness when re-used.

The mixture of water and clarifying agent can be readily filtered, or can be de-watered by other methods in order to separate the clarified water from the residual solids. The settled solids may be wet-incinerated, dried, dry-incinerated, etc., used for land-fill, fertilizer, soil-builder, or otherwise used. They can be transported for ultimate disposal in a now-concentrated form, recycled in the same or other process, or otherwise discarded.

In the case of municipal waste water treatment, the settled solids and/or dewatered solids may be readily converted into an acceptable form of soil nutrient.

The materials herein elucidated as clarifying agents for water are biologically inocuous; they do not create ecological or toxicological problems in the water treated therewith. The chemical oxygen demand (C.O.D.) and biological oxygen demand (B.O.D.), and

,hence the total oxygen demand of these new flocculating agents are nil, of course, because they are already oxidized to an extent greater than that attainable at any temperature range in the liquidous state of water under reasonable pressures.

The following examples are given in order to merely illustrate the invention, and are not to be construed as limiting the invention in any way.

EXAMPLE I Tricalcium aluminate was prepared by dissolving 18.12 g (0.02 mole) of ammonium alum in water and making the solution up to a total of 50.0 g, followed by reaction with an excess of ammonium hydroxide. The aluminum hydroxide so produced was filtered and washed until free of excess ammonium hydroxide, and then redispersed in water. To this dispersion was added 3.36 g (0.06 mole) of calcium oxide, and the mixture thoroughly mixed, dried on a hot plate until a paste of the finely divided solids resulted. This was placed in a platinum crucible and the physically bound water driven off by heating. An oxygen acetylene torch was then used to heat and fuse the contents of the crucible at white heat, producing a homogenous light yellow glassy material. This was removed from the crucible, crushed into fine particles, and stored in a stoppcred bottle. This product is that referred to as tricalcium aluminate, (fused)" in the Examples.

In similar reactions at white heat, dicalcium silicate was formed by fusion together of 3.1 parts of silica sand with 4.4 parts of calcium oxide; tricalcium silicate by fusion together of 4.96 parts of calcium oxide with 2.8 parts of silica sand, zinc aluminate by fusion of the analogous zinc product as above for preparation of tri calcium aluminate, and magnesium aluminate by the same method, following coprecipitation of 1.4 parts sodium aluminate with 2.3 parts of hydrated magnesium sulfate from aqueous solution.

EXAMPLE II To 50 milliliters of a typical activated sludge obtained from the secondary stage of a municipal waste treatment plant was added 0.14 g of powdered tricalcium aluminate (fused). The solids in the activated sludge flocculated. In similar tests, dicalcium aluminate, zinc aluminate, magnesium aluminate, sodium ferrite, calcium ferrite, and dicalcium silicate were used to treat activated sludge.

EXAMPLE III A series of experiments were carried out using some of the flocculating agents herein concerned, as tricalcium aluminate, and a powdered cement containing 40% calcium aluminante, in comparison with known flocculating agents, viz.: alum, ferric chloride, ferric chloride plus lime, sodium aluminate and ferric chloride sodium hydroxide, as settling agents for the solids in activated sludge as above described in Example II. One hundred milliliters of the treated sludge containing these agents was allowed to settle for 10 minutes (600 seconds) and the volume of clear supernatant recoverable water observed and recorded. The results are given in Table 1.

In a similar test, tri-calcium aluminate (fused), tricalcium aluminate (as prepared), 40% tri-calcium aluminate cement, prepared from ca. 40% tri-calcium aluminatc, ca. tri-calcium silicate, and ca. 10% tricalcium silicate fused togethcr. cooled, and pulverized (I-ITCAC), and calcium borate, the new flocculants concerned herein, were compared with the known, conventional flocculant Alum when used to clarify an activated sludge such as described in Example II. The results are given in Table 2.

TABLE 2 CLARIFYING AGENT AMOUNT CLARIFIED VOLUME g/l00 ml ml at 600 sec.

Tricalcium Aluminate 0.5 l7. (fused) 'l'ricalcium Aluminate 0.5 12. (as prepared) Calcium Borate 0.5 9,

40% Tricalcium Aluminate 0.5 6

Portland Cement 0.5 3.

Alum 0.5 l.

Blank l EXAMPLE IV A comparison was made of filtration rates of untreated activated sludge as described in Example II with the rate obtained when it was treated with a typical clarifying agent of the invention and when treated with the conventional inorganic flocculating agents. The data are given in Table 3.

TABLE 3 FLOCCULANT AMOUNT FILTRATION RA'I'F.

g/l00 ml (7? of volume total/see) Tricalcium Aluminate 0.273 30.] Alum 0.5 2L7 Ferric Chloride Lime 0.2 I 16.8 Sodium Aluminatc 0.52 3.96 BLANK 13 6.88

Additional work was done comparing the filtration volume at 400 seconds in percent of original volume of sludge. The tricalcium aluminate clarifying agent of this invention was compared with conventional inorganic flocculating agents of commerce. These data were obtained by methods given in the description of Example IV. The results are tabulated in Table 4.

A set of experiments was carried out inwhich a comparison was made to-show the effect of the valence of 6 EXAMPLE VI In an experiment in which a comparison was made of the efficacy of fused-" with unfusedclarifying agents of the invention, an activated sludge similar to that described in Example II was treated with bothtypes of material. The data obtainedare given in Table 6.

TABLE 6 C LARIFIED FLQCCUI..ANT TREAT- VOLUME MOUNT MENT g/IOO ml at ml 600 seconds BLANK I. Fri-calcium Aluminate Unfused 0.5 12. Tri-calcium Aluminate Fused 0.5 I7. i 40% 'Iricalcium Unfused 0.34 4.'

' Aluminate Cement" HTCAC 40% 'l'ricalcium Fused 0.34 6.

Aluminate Cement HTCAC' EXAMPLE VII A study similar to that described in Example VI was carried out in which several inorganic flocculants were compared. The data given in Table 7 again shows the efficiency of the polyvalent ion compounds of the in-v vention are characteristic of this group of elements.

the positive ion of the inorganic clarifying agent upon TABLE 7 the clear volume obtained ten minutes after treatment of activated sludge with aluminates and ferrites of FLOCCULAN'I' AMOUNT CLARll-IED mono-and di-valent ions. This shows the marked supe- VOLUME 4() g/IOO ml ml at 600 seconds -r1or1ty of the poly-valent ion compounds of this invention over the mono-valent ion compounds of the con- BLANK I I d I Magnesium Alummate 0.5 9. ventional flocculatmg agents. These ata are given m Zinc A'umi'nute 05 8 Table 5. MIXTURE Synthetic" Calcium Aluminosilicate 0.5 I2. TABLE 5 (Calcium silicate-Calcium Aluminate) Portland Cement 0.5 5.

, CLARIFIED FLOCCULANT VALENCF. VOLUMF.

MOUNT g/l00 OF ml at ml ION 600 seconds I 5() EXAMPLE VIII BLANK l. Sodium Aluminute 0.5 l A series of experiments were carried out in which the Tricalcium Aluminatc 0.5 2 l7. I Q Sodium Femw (L54 1 0: add tion of a fine clay was added to the mixture of the Calcium Ferrite 0.5 2 2. clarifying agents of the invention and the activated li'relffnlldl tiulinldntillc i 55 sludge described in Example II. The data show the effi- CI'I'IL umln' 8 A cacy of this refinement, and are tabulated in Table 8.

TABLE 8 FLOCCULANT AMOUNT ADDITIVE AMOUNTCLEAR VOLUME g/l00 ml g/tesl ml at 600 sec.

BLANK Tricalcium Aluminate 0.5 4. do. I 0.5 Clay 0.5 31. Calcium Aluminosilicate 0.5 l2. do. 0.5 Clay 0.] 40. do. 0.5 Volcanic ().l 59.

Ash

TABLE 8 Continued FLOCCULANT AMOUNT ADDlTlVE AMOUNT CLEAR VOLUME g/lOO ml. g/test ml at 600 sec.

407: Tri-calcium Aluminate Cement" HTCAC 0.5 Clay ().l 27. Alurn 0.5 A l. Ferric Chloride Lime 0.2 0.05 3. Clay 0.5 t). Volcanic Ash 0.5 0.

EXAMPLE lX TABLE 9 Aset of experiments was carried out using the inorganic flocculants of the invention to treat tanncry waste H'OCCULANT AMOUN'I bS and to treat brewery wastes. To lOO milliliter portions 15 EH ml m| at 6 l of each waste were added 0.1 g of tricalcium aluminatev Flocculation of material in the wastes took place in the BLANK i Sodium Alummate l) 0.5 1. case of both types of waste, the tannery waste and the Ferric Chlmidc Lime U brewery waste. Upon filtration of the flocculated mix- Portland Cement 1.0 6. 'lricalcium Alurninate 05 I2.

tures, essentially uncolored filtrate was obtained in both cases. 1

EXAMPLE X A comparison was made of the clear supernatant volume produced by the flocculants taught as part of this invention and the volumes produced by using conventional inorganic flocculants. The various materials were mixed with the activated sludge described in Example ll, and allowed to stand for IO minutes. The volumes of clear supernatant were recorded and are givven in Table 9. This experiment shows that these new flocculants are superior to the conventional types in respect to the ability to'clear water of sludge solidswithout filtering. 

1. THE PROCESS FOR PURIFICATION OF WATER WHICH COMPRISES THE MIXING OF IMPURE WATER WITH A WATER-HYDRATABLE MATERIAL CONSISTING ESSENTIALLY OF MAGNESIUM. AND COPPER, PRESELECTED FROM THE GROUP CONSISTING OF MAGNESIUM, CALCIUM, STRONTIUM, ZINC, CADMIUM, IRON, MANGANESE, AND COPPER, PREPARED BY FUSION OF RAW MATERIALS CONTAINING THEN OPTIONALLY WITH DENSITY-REGULATING MINERALS HAVING AT LEAST SOME ION-EXCHANGE CHARACTERISTICS. 